Joseph annaheim



NITED STATES PATENT rrica JOSEPH ANN AHEIM, OF BASLE, SWITZERLAND, ASSIGNOR TO L. DURAND 8t HUGUENIN, OF SAME PLACE.

MANUFACTURE OF BLUE COLORING-MATTER.

SPECIFICATION forming part of Letters Patent No. 369,764, dated September 13. 1887.

Application filed November 4, 1896. Serial No. 217,971. (SpecimensJ Patented in France September 6, 1886, No. 179,364, and in England November 5, 1886, No. 14,283.

To alZ whom it may concern:

Be it known that I, JOSEPH ANNAHEIM, doctor of philosophy, a citizen of Switzerland, residing at 58 St. Johannvorstadt, Basle, Switzerland, have invented certain new and useful Improvements in the Manufacture of Dyeing-Matter, (for which Letters Patent have been issued in Great Britain, N 0. 14,283, dated November 5, 1886, and in France, No. 178,364, dated September 6, 1886 5) and I do hereby declare the following to be a full, clear, and exact description of the invention, such as will enable others skilled in the art to which it appertains to make and use the same.

The invention relates to the manufacture of coloring-matter; and it consists in a novel process of obtaining reddish-violet to blue coloring-matterby treating the nitroso derivates of the tertiary aromatic amines with the bioxy- 2o naphthalines and the products of condensation of the bioxynaphthalines with aniline or one of the homologues of the latter, substantially as hereinafter fully described, and as set forth in the claims.

1. o,,H,:8g+c,H,NH,=

5.5 Oxyphenyl-naphthylamine, water,

As shown by experiment, it seems that the reaction seems to take place principally according to the second equation, under the con- (lit-ions hereinafter set forth--that is to say,

both the hydroxyl groups are replaced by l phenylamide residues or remainders, O H Nlil. of aniline may readily be deduced.

The following may be used as condensing agents: chloride of calcium, chloride of zinc,

and hydrochloric acid, either by themselves The invention further consists in a new arti- 25 cle of manufacture from which coloring-mam ter can be obtained, substantially as hereinafter described, and as set forth in the claims.

The formation of the products of condensation of bioxynaphthaline with aniline and its homologues is effected as follows: If a con densing agent is mixed with bioxynaphthaline and a primary aromatic amine, such as aniline, para or ortho toluidine, xylidine, or cumidine, or alpha or beta naphthylamine, 850., and the, mixture is heated, water is separated; and when aniline is used the following products are obtained:

Oxyphenylnaphthylamine, O E -OH -NO H,, 43

H Diphenyl naphthyldiamine, G, H NO,,H,, 5

according to the equations-' Bioxynapht-haline, aniline.

OI-I

Bioxynaphthaline, aniline:

Dyphenyl-naphthyldiamine.

or in the form of amine hydrochloratc or chloride of aluminium, 8m.

As an example, I will only give the production of the aniline derivates from which the production of the derivates of the homologues I mix sixteen kilograms of bioxynaphthaline (preferably that prepared according to the process of Ebert 8E Mertz, Reports of the German Society 35 ,7 by either of the following methods:

of Chemists, Berichteder Deutschen Chemischen Gesellschaft,'volume ix, page 609) with thirty-seven kilograms of aniline and thirteen kilograms of aniline hydrochlorate, and heat the mixture, either in a closed or an open vessel, to the boiling-point of the aniline. When the reaction is completed, the mass is treated in the usual manner to eliminate the aniline therefrom. The product, free from aniline, is then purified and compressed and dried.

As the above-described proportions may be varied and equally good results obtained, I do not desire to limit myself thereto.

The new combination obtained, as described, is a solid white bgdy, insoluble in water, and in the alkalies not'readily soluble in cold ethyl,

- methyl, or amyl alcohol, easily solublein ether,

boiling benzole, toluol, or glacial acetic acid, and by means of these solvents the-product may be readily obtained in a chemically pure crystalline form. The meltingpoint of this product is 163.5 centigrade. The toluidine and xylidine derivates may be obtained with equal facility. \Vhen alpha or beta naphthylamine isemployed, the reaction takes place under less favorable conditions in that the formation of dinaphthylamine is observable to a disagreeable degree.

The product obtained from paratoluidine is considerably less soluble in the above-named solvents than the aniline derivates, and its melting-point is considerably highernamel y, 237. From these products of condensation I obtain reddish-violet to blue coloring-matter, according to the combination of chemicals,

First, by mixing the products of condensation, preferably in molecular proportiomwith the free nitroso combination, or a salt thereof as, forinstance, nitroso-dimethylaniline hydrochlorateand a suitable solvent, and gradually heating the compound until the complete conversion of the product into coloring-matter has been effected. The following solvents may be employed: a weak alkaline (neutral or acid) aqueous solution, and, if the alkaline solution is an acid one, I preferably employ an acetate; or alcohols, glacial acetic acid, &c.,

may be employed. v

Secondly, by reducing the nitroso combina tionfor instance, nitroso-dimethylaniline hydrochloratewith zinc-dust and hydrochloric acid, adding thereto the binoxynaphthaline and oxidizing the mass by the addition of hichromate of potassium or sesquichloride of sation of bioxynaphthaline with aniline or one of its homologues, substantially as described.

3. The process of obtaining coloring-matter from the product of condensation of bioxynaphthaline with aniline or one of its homologues, by treating the product directly with nitroso combinations of the tertiary aromatic amines, or by reducing the nitroso combinations and oxidizing the resulting diamine and the product of condensation, substantially as described.

In testimony whereof I affix my signature in presenceof two witnesses.

JOSEPH ANNAHEIM.

Witnesses:

J AKOB FRANK, GEORGE GIFFORD. 

